Polymerization of olefins

Details Polymerization of olefins Polymerization of olefins

2000-09-28

2002-06-18

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S115000, C526S117000, C526S118000, C526S119000, C526S161000, C526S169100, C526S172000

Reexamination Certificate

active

06407188

ABSTRACT:

FIELD OF THE INVENTION
Polymers with varied and useful properties may be produced in processes using at least one polymerization catalyst, and at least one oligomerization catalyst for ethylene which is a selected iron catalyst.
TECHNICAL BACKGROUND
Polyolefins are most often prepared by polymerization processes in which a transition metal containing catalyst system is used. Oftentimes, these transition metal catalysts will copolymerize two olefins such as ethylene and an &agr;-olefin, especially a higher &agr;-olefin. Such copolymers have been found very useful in a large number of fields; however, the higher cost of the &agr;-olefin is a negative for these types of polymers compared to polymers made only from cheap olefins such as ethylene or propylene.
Various reports of “simultaneous” oligomerization and polymerization of ethylene to form (in most cases) branched polyethylenes have appeared in the literature, see for instance WO90/15085, WO 99/50318, U.S. Pat. Nos. 5,753,785, 5,856,610, 5,686,542, 5,137,994 and 5,071,927; C. Denger, et al,
Makro
-
mol. Chem. Rapid Commun.,
vol. 12, p. 697-701 (1991); and E. A. Benham, et al.,
Polymer Engineering and Science,
vol. 28, p. 1469-1472 (1988). None of these references specifically describes any of the processes or resulting branched polyolefins herein.
SUMMARY OF THE INVENTION
This invention concerns a process for preparing a branched polyolefin, comprising the steps of:
(1) contacting an ethylene oligomerization catalyst and a first monomer component comprising ethylene, under conditions to oligomerize at least a portion of the ethylene to one or more even &agr;-olefins of the general formula R
28
CH═CH
2
wherein R
28
is alkyl containing an even number of carbon atoms, wherein the ethylene oligomerization catalyst comprises an active Fe complex of a ligand of the formula (I):
wherein:
R
1
, R
2
, R
3
, R
4
and R
5
are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group, provided that any two of R
1
, R
2
and R
3
vicinal to one another, taken together may form a ring; and
R
6
and R
7
are aryl or substituted aryl; and
(2) contacting an active transition metal copolymerization catalyst, with a second monomer component comprising ethylene, at least a portion of the &agr;-olefin from step (1) and an odd &agr;-olefin of the formula R
18
CH═CH
2
wherein R
18
is alkyl containing an odd number of carbon atoms, under conditions to copolymerize the ethylene, even &agr;-olefin and odd &agr;-olefin to a branched polyolefin.
The two steps of the above-mentioned process may occur separately, sequentially and/or simultaneously, as described in further detail below.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Herein certain terms are used which are defined below.
By “hydrocarbyl” is meant a univalent radical containing only carbon and hydrogen. As examples of hydrocarbyls may be mentioned unsubstituted alkyls, cycloalkyls and aryls. If not otherwise stated, it is preferred that the hydrocarbyl groups herein contain 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms.
By “substituted hydrocarbyl” herein is meant a hydrocarbyl group that contains one or more “inert functional groups” that are inert under the process conditions to which the compound containing these groups is subjected. The inert functional groups also do not substantially interfere with the oligomerization/polymerization process. For example, in cases in which the inert functional group may be near the complexed iron atom, such as R
4
or R
5
in (I), or as a substituent on R
4
, R
5
, R
6
or R
7
, the inert functional group should not coordinate to the iron atom more strongly than the three depicted N groups in (I) which are the desired coordinating groups—that is, the functional group should not displace one or more of the desired coordinating N groups. The hydrocarbyl may be completely substituted, as in trifluoromethyl. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of “substituted” are heterocyclic rings.
Examples of inert functional groups include halo (fluoro, chloro, bromo and iodo), ester, keto (oxo), amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, amide, nitrile, and ether. Preferred inert functional groups are halo, ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, and amide. Which inert functional groups are useful in which oligomerizations/polymerizations may in some cases be determined by reference to U.S. Pat. Nos. 5,955,555, 6,103,946 and WO98/30612, all of which are hereby incorporated by reference for all purposes as if fully set forth.
By an oligomerization or polymerization “catalyst activator” is meant a compound that reacts with a transition metal compound to form an activated catalyst species. A preferred catalyst activator is an alkylaluminum compound, that is, a compound which has at least one alkyl group bound to an aluminum atom.
By “relatively noncoordinating” (or “weakly coordinating”) anions are meant those anions as are generally referred to in the art in this manner, and the coordinating ability of such anions is known and has been discussed in the literature. See, for instance, W. Beck et al.,
Chem. Rev.,
vol. 88, pp. 1405-1421 (1988), and S. H. Strauss,
Chem. Rev.,
vol. 93, pp. 927-942 (1993), both of which are hereby included by reference. Among such anions are those formed from aluminum compounds (such as those described in the immediately preceding paragraph) and X
−
(an anion as discussed in further detail below), including (R
19
)
3
AlX
−
, (R
19
)
2
AlClX
−
, R
19
AlCl
2
X
−
, and R
19
AlOX
−
, wherein R
19
is alkyl. Other useful noncoordinating anions include BAF
−
{BAF=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate}, SbF
6
−
, PF
6
−
, and BF
4
−
, trifluoromethanesulfonate, p-toluenesulfonate, (R
f
SO
2
)
2
N
−
, and (C
6
F
6
)
4
B
−
.
By a “primary carbon group” herein is meant a group of the formula —CH
2
———, wherein the free valence ——— is to any other atom, and the bond represented by the solid line is to a ring atom of an aryl or substituted aryl to which the primary carbon group is attached. Thus the free valence ——— may be bonded to a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a sulfur atom, etc. In other words, the free valence ——— may be to hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group. Examples of primary carbon groups include —CH
3
, —CH
2
CH(CH
3
)
2
, —CH
2
Cl, —CH
2
C
6
H
5
, —OCH
3
and —CH
2
OCH
3
.
By a secondary carbon group is meant the group
wherein the bond represented by the solid line is to a ring atom of an aryl or substituted aryl to which the secondary carbon group is attached, and both free bonds represented by the dashed lines are to an atom or atoms other than hydrogen. These atoms or groups may be the same or different. In other words the free valences represented by the dashed lines may be hydrocarbyl, substituted hydrocarbyl or inert functional groups. Examples of secondary carbon groups include —CH(CH
3
)
2
, —CHCl
2
, —CH(C
6
H
5
)
2
, cyclohexyl, —CH(CH
3
)OCH
3
, and —CH═CCH
3
.
By a “tertiary carbon group” is meant a group of the formula
wherein the bond represented by the solid line is to a ring atom of an aryl or substituted aryl to which the tertiary carbon group is attached, and the three free bonds represented by the dashed lines are to an atom or atoms other than hydrogen. In other words, the bonds represented by the dashed lines are to hydrocarbyl, substituted hydrocarbyl or inert functional groups. Examples of tertiary carbon groups include —C(CH
3
)
3
, —C(C
6
H
5
)
3
, —CCl
3
, —CF
3
, —C(CH
3
)
2
OCH
3
, —C≡CH, —C(CH
3
)
2
CH═CH
2
, aryl and substituted aryl such as phenyl and 1-adamantyl.
By “aryl” is meant a monovalent aromatic group in which the free valence is to the carbon

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